CN1039600A - The acetal copolymers that bromo functional groups is arranged on the main chain - Google Patents
The acetal copolymers that bromo functional groups is arranged on the main chain Download PDFInfo
- Publication number
- CN1039600A CN1039600A CN89102216A CN89102216A CN1039600A CN 1039600 A CN1039600 A CN 1039600A CN 89102216 A CN89102216 A CN 89102216A CN 89102216 A CN89102216 A CN 89102216A CN 1039600 A CN1039600 A CN 1039600A
- Authority
- CN
- China
- Prior art keywords
- main chain
- bromo
- functional groups
- halogen
- trioxane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D321/00—Heterocyclic compounds containing rings having two oxygen atoms as the only ring hetero atoms, not provided for by groups C07D317/00 - C07D319/00
- C07D321/02—Seven-membered rings
- C07D321/04—Seven-membered rings not condensed with other rings
- C07D321/06—1,3-Dioxepines; Hydrogenated 1,3-dioxepines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G4/00—Condensation polymers of aldehydes or ketones with polyalcohols; Addition polymers of heterocyclic oxygen compounds containing in the ring at least once the grouping —O—C—O—
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Polyethers (AREA)
Abstract
The present invention relates to a kind of method of making the acetal copolymer that bromo functional groups is arranged on the main chain, it comprises three alkane and 5,6-two bromo-1, and the 3-Dioxepane carries out copolymerization.The invention still further relates to the acetal copolymers method of modification and the multipolymer that makes with the inventive method in addition that will contain bromo functional groups.
Description
The polyacetals multipolymer is the macromole with industrial value, and they can same metal in a lot of practical applications, pottery is competed mutually with nylon.According to present processing method, they are that Yong trioxane and a kind of comonomer such as oxyethane, dioxolane or butyleneglycol formal make through copolymerization.Each molecule of this multipolymer has two functional groups at most, as terminal hydroxy group.To getting on very well, preferably synthesize the higher polyacetals of functional group content such as the polymkeric substance of preparation graft copolymer and band Chemical bond stablizer.The objective of the invention is to prepare the polyacetals multipolymer of trioxane, its stability will be equivalent to or be higher than resin commonly used, has the functional group that can be used to further modification or link additive simultaneously again.
In common Derlin product, the additive such as the amidine thermo-stabilizer tends to exist in the pars amorpha of polymkeric substance.Because this noncrystalline domain is random from macroscopic property in spatial distributions, the distribution of this additive usually is not optimum.If the part of functional group can just can make stablizer or impact modifying agent be attached at the locus of being scheduled in the resin by well-regulated or half well-regulated spacing setting (as random copolymers), the uniform nature more just can obtain good like this.Because the crystalline structure of polyacetal makes additive block crystallizing field from the space, this method is especially effective.Therefore, it would be desirable that the part that constitutes main polymer chain can be blocked the crystalline structure of polymkeric substance by controllable mode, and provide the locus for linking additive.
Polyacetals multipolymer with this main chain functional group can be useful in a lot of important practical applications, such as: a) preparation contains chemical bonding stablizer De trioxane multipolymer;
B) preparation contains chemically combined impact modifying agent De trioxane multipolymer; C) graft copolymer of preparation trioxane, as with the compatilizer of existing commercially available acetal copolymer mixture, or with the compatilizer of other polymer materials such as glass or mineral; D) preparation can be accepted the multipolymer of surface modification; E) preparation crosslinked copolymers.
The present invention relates to a kind of method for preparing the acetal copolymer of halogen-containing functional group on the main chain.Certain preferred embodiment relates to the method that a kind of preparation contains the multipolymer of bromo functional groups, and this method comprises with trioxane and 5,6-two bromo-1, and 3-dioxane heptene carries out copolymerization.
The invention still further relates to the acetal copolymers that makes with this new method and the further modification of these multipolymers.
Embodiment 1
A) monomeric synthetic:
1,3-dioxane heptan-5-alkene, DXPE
With 176 gram (2 moles) cis-2-butenes-1, the 4-glycol, 60 gram (2 moles) Paraformaldehyde 96s, the mixture of 25 milliliters of benzene and 0.25 gram tosic acid refluxes by a Dean-Rodney Stark (Dean-Stark) water trap and removes fully until water.Reaction mixture distills after taking off benzene and obtains 172 grams 1,3-dioxy penta-5-alkene (120～126 ℃ of boiling points) crude product.This crude product that contains less water and formaldehyde is once made with extra care by redistillation from solid potassium hydroxide.Obtain 160 grams 1, the straight product of 3-dioxy penta-5-alkene (boiling point=130 ℃).
Embodiment 2
5,6-two bromo-1,3-Dioxepane
With 15.2 gram (0.15 moles) 1, the 3-dioxane heptan-solution of 5-alkene in 20 milliliters of tetracol phenixin places ice bath to cool off.Under agitation dropwise add the solution of 24 gram (0.15 mole) bromines in 20 milliliters of tetracol phenixin then.Then remove with distillation and desolvate, the residue ethyl alcohol recrystallization makes 8.1 grams 5,6-two bromo-1, and 3-Dioxepane, fusing point are 37 ℃.
Embodiment 3
Three alkane and 5,6-two bromo-1, the copolymerization of 3-dioxolane
In exsiccant flask (Kjeldahl, 100 milliliters), put into 10 gram trioxanes and 2.5 grams 5,6-two bromo-1,3-Dioxepane.Bottle covers with soft rubber ball.Under vacuum, remove after the air and dissolved gases in the reaction mixture, use the nitrogen wash flask.With bottle place oil bath (60～65 ℃) with magnetic stirrer with the thing fusion of bottle and mix.Then by soft rubber ball toward bottle in be injected into the boron trifluoride etherate of 0.2 microlitre.Solution is from the brown white that becomes.This solution did not become mobile owing to polymer growth spreads all over whole flask within about 30 minutes.Make and be reflected at 60 ℃ and carried out 20 hours.Polymerization finishes promptly to shift out polymkeric substance and be ground into fritter.9.5 the gram crude product is used methanol wash three times more earlier with the 10 ml methanol solution washings that contain 2% trolamine.Obtain 9 gram multipolymers 40 ℃ of vacuum-dryings.
This multipolymer is very easy generation radical under UV-irradiation.The photosensitivity that it is had by the shown multipolymer of electron spin resonance absorption can be used for the photochemical modification of polymkeric substance, as surface grafting.The present invention also attempts to prepare with the comonomer of other halogen such as the chlorine modification.Also can prepare according to method of the present invention has the acetal copolymers of halogen functional group such as chlorine De trioxane on the main chain.The photosensitivity of bromine atoms and chlorine atom pairs UV-light and high-energy irradiation adds zip mode (unzipping) characteristic that acetal copolymer itself has, and halogen modified multipolymer of the present invention be can be used as make the photo-resist that unicircuit is used.
Claims (8)
1, a kind of method of making the acetal copolymer of halogen-containing functional group on the main chain, it comprises carries out copolymerization Jiang the compound of trioxane and following formula,
Wherein, R is a halogen.
2, the acetal copolymer that makes according to the method for claim 1.
3, a kind of method of making the acetal copolymer that contains bromo functional groups on the main chain, it comprises trioxane and 5,6-two bromo-1,3-dioxane heptene carries out copolymerization.
4, the acetal copolymer that makes according to claim 3.
5, a kind of photo-resist of making by the polyacetal of halogen-containing functional group on the main chain.
6, according to the photo-resist of claim 5, halogen wherein is a bromine.
7, according to the photo-resist of claim 5, halogen wherein is a chlorine.
8, according to the photo-resist of claim 5, wherein, polyacetal Shi trioxane and 1, a kind of multipolymer of 3-dioxy penta-5-alkene or derivatives thereof.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/181,237 US4906728A (en) | 1988-04-13 | 1988-04-13 | Acetal copolymers with backbone bromo functional groups |
| US181,237 | 1988-04-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1039600A true CN1039600A (en) | 1990-02-14 |
Family
ID=22663444
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN89102216A Pending CN1039600A (en) | 1988-04-13 | 1989-04-12 | The acetal copolymers that bromo functional groups is arranged on the main chain |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4906728A (en) |
| EP (1) | EP0337754A3 (en) |
| JP (1) | JPH0211629A (en) |
| KR (1) | KR890016037A (en) |
| CN (1) | CN1039600A (en) |
| BR (1) | BR8901747A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5206308A (en) * | 1989-05-12 | 1993-04-27 | Hoechst Celanese Corporation | Grafting of amine functional polymers onto functionalized oxymethylene polymers and the resulting graft polymers thereof |
| JPH0761337A (en) * | 1993-08-26 | 1995-03-07 | Aisin Seiki Co Ltd | Brake device with retract mechanism for wheel brake |
| US20020037472A1 (en) * | 2000-09-08 | 2002-03-28 | Shipley Company, L.L.C. | Novel polymers and photoresist compositions comprising labile polymer backbones for short wave imaging |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA720516A (en) * | 1965-10-26 | Farbwerke Hoechst Aktiengesellschaft Vormals Meister Lucius And Bruning | Trioxane-1,3-dioxepane copolymers | |
| US3337587A (en) * | 1960-03-21 | 1967-08-22 | Union Carbide Corp | 2-hydrocarbon-5, 6-epoxy-1, 3-dioxepanes |
| NL271273A (en) * | 1960-11-15 | |||
| BE631682A (en) * | 1962-04-28 | |||
| DE2062958A1 (en) * | 1970-01-23 | 1971-07-29 | Perstorp Ab | Process for the production of stable trioxane copolymers |
| BE787798A (en) * | 1971-08-19 | 1973-02-21 | Hoechst Ag | PROCESS FOR PREPARATION OF HOMOPOLYMERS AND COPOLYMERS OF CYCLIC ACETALS |
| US4399272A (en) * | 1979-11-15 | 1983-08-16 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for producing polyacetal copolymers |
| US4751272A (en) * | 1986-05-01 | 1988-06-14 | Toray Industries, Inc. | Process for producing oxymethylene copolymer and resinous composition |
-
1988
- 1988-04-13 US US07/181,237 patent/US4906728A/en not_active Expired - Lifetime
-
1989
- 1989-04-12 CN CN89102216A patent/CN1039600A/en active Pending
- 1989-04-12 KR KR1019890004831A patent/KR890016037A/en not_active Application Discontinuation
- 1989-04-12 JP JP1092775A patent/JPH0211629A/en active Pending
- 1989-04-12 BR BR898901747A patent/BR8901747A/en not_active Application Discontinuation
- 1989-04-12 EP EP89303605A patent/EP0337754A3/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| BR8901747A (en) | 1989-11-28 |
| JPH0211629A (en) | 1990-01-16 |
| EP0337754A3 (en) | 1990-03-14 |
| EP0337754A2 (en) | 1989-10-18 |
| US4906728A (en) | 1990-03-06 |
| KR890016037A (en) | 1989-11-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |